WO2017205286A1 - High strength shaped aluminas and a method of producing such high strength shaped aluminas - Google Patents

High strength shaped aluminas and a method of producing such high strength shaped aluminas Download PDF

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Publication number
WO2017205286A1
WO2017205286A1 PCT/US2017/033831 US2017033831W WO2017205286A1 WO 2017205286 A1 WO2017205286 A1 WO 2017205286A1 US 2017033831 W US2017033831 W US 2017033831W WO 2017205286 A1 WO2017205286 A1 WO 2017205286A1
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WO
WIPO (PCT)
Prior art keywords
alumina
alumina powder
particle size
powder
ppm
Prior art date
Application number
PCT/US2017/033831
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English (en)
French (fr)
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WO2017205286A9 (en
Inventor
David A. Barclay
Mark M. Chavez
Original Assignee
Sasol (Usa) Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority to US16/099,397 priority Critical patent/US11091396B2/en
Application filed by Sasol (Usa) Corporation filed Critical Sasol (Usa) Corporation
Priority to KR1020187037534A priority patent/KR102366730B1/ko
Priority to EP17729593.8A priority patent/EP3464215A1/en
Priority to CA3024172A priority patent/CA3024172A1/en
Priority to JP2018561486A priority patent/JP7042754B2/ja
Priority to CN201780031401.5A priority patent/CN109476550A/zh
Priority to RU2018144008A priority patent/RU2759835C2/ru
Publication of WO2017205286A1 publication Critical patent/WO2017205286A1/en
Publication of WO2017205286A9 publication Critical patent/WO2017205286A9/en
Priority to US17/366,277 priority patent/US11884594B2/en

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    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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Definitions

  • THIS INVENTION relates to a method of producing high strength shaped alumina and to a shaped alumina having low impurities, high strength, controlled porosity and high loose bulk density.
  • High strength shaped alumina in the form of beads, spheres, spherical particles, or agglomerates, for example, are used in numerous applications such as oil field chemical carriers, catalyst supports and catalysts, fillers for refractories and polymers, and proppant particles for oil field use.
  • Shaped alumina with high bulk density is used in making synthetic sapphire by crucible melting processes.
  • Shaped alumina for example beads, is normally produced by making a dispersion or sol with feedstock alumina, spraying or dropping the dispersion or sol to form beads, drying the beads to remove water and making the beads strong enough for additional processing, followed by calcining at high temperatures to create a gamma or sintered alpha alumina with high strength and high bulk density. These processes require expensive forming and drying steps due to the large amount of water needed to create the alumina dispersions.
  • Subsequent conversion to alpha alumina requires high temperature calcination or seeding with alpha alumina to lower the alpha conversion temperature and reduce the cost of sintering the bead to a bead having a low porosity, high density and thus a high strength.
  • a possible way to reduce the cost of making such beads is to incorporate a spray drying step into the above described process, however such an improvement to the process still limits the bead size to the ability of a spray dryer nozzle to spray droplets into a dryer and get them dried before exiting the dryer.
  • Calcination is also still needed to create strong, dense granules.
  • Another method to form alumina beads is a modified drying and agglomeration process which sprays an alumina dispersion onto a fluidized bed of particles to build up the size of the beads while removing water or solvent.
  • Extrusion plus spheronization processes are other known methods which do not use as much liquid as the dropping or spray drying methods but do require up to 40% to 50% liquid to transform alumina into a pliable or plastic mass which can be shaped by forcing it through a die or extruder.
  • the alumina paste is extruded through a die plate or extruder to create a cylindrical shape which is formed into beads by a high speed tumbling device which breaks the cylinders into pieces and rounds these into beads with the same diameter as the extruded cylinders.
  • the beads must then be dried and calcined to have high strength and a high bulk density.
  • the invention of the present application overcomes the problems with an agglomeration process that produces high strength, high density shaped alumina at a lower cost and with fewer processing steps than other forming processes.
  • a method to produce high strength shaped alumina comprising: i) feeding alumina powder into an agglomerator, the agglomerator including a shaft with mixers able to displace the alumina powder along a length of the shaft,
  • the shaped alumina may be in the form of agglomerates, beads or spherical particles.
  • agglomerator is meant a chamber including a central shaft having mixers thereon.
  • the mixers are preferably in the form of pins or paddles located along a length of the shaft.
  • Alumina powder is preferably displaced along a length of the shaft by rotation of the shaft and action of the pins or paddles to move the alumina powder or shaped alumina along the axis of rotation.
  • the shaft rotates continuously such that the mixers are able to firstly break down an alumina powder and then re-agglomerate the alumina powder as the alumina powder is displaced along the length of the shaft of the agglomerator.
  • the agglomerator is preferably a high shear agglomerator. Examples of such high shear agglomerators include a pin mixer, a Turbulizer ® mixer (a continuous high shear paddle mixer), or a mixer manufactured by Lodige.
  • the alumina powder may comprise an aluminum oxide hydroxide (AIOOH), a boehmite, or a pseudoboehmite, preferably a boehmite.
  • AIOOH aluminum oxide hydroxide
  • boehmite a boehmite
  • pseudoboehmite preferably a boehmite.
  • the alumina powder may have a crystallite size of 35A to 190 A and a particle size D50 value of greater than or equal to 40 micron.
  • crystallite size refers to the size measurement on the 021 plane as measured by x-ray diffraction using the Scherer equation to determine the crystallite size.
  • D50 value is meant the "median” meaning that 50% of all particles are smaller than the size described and 50% are larger than the size described.
  • the particle size D50 value is determined by laser scattering with a Malvern Mastersizer 2000 particle size analyzer. Examples of suitable alumina are Sasol's Catapal ® B, Catapal ® C1 , Catapal ® D, and Ultra High Purity Alumina having a crystallite size of 35A to 190A.
  • the method further includes the initial step of milling the alumina powder before feeding the alumina powder into the agglomerator to an average particle size D50 value of less than 40 microns, preferably an average particle size D50 value of 30 microns, and more preferably an average particle size D50 value of 10 microns or smaller.
  • the alumina powder may have a crystallite size of 300 A to 500 A, preferably from 325 A to 450 A.
  • aluminas are chosen as a feedstock to the process of the present invention, no milling step is required.
  • examples of such an alumina are Sasol's Catapal® 200 alumina, Pural® 200 alumina, and Ultra High Purity Alumina having a crystallite size of 300A to 500A.
  • the invention provides for a third option, including a combination of i) milling the alumina powder having a crystallite size of between 35 A and 190 A and a particle size Dso value of greater than or equal to 40 microns to an average particle size D50 value of less than 40 microns, preferably an average particle size D50 value of 30 microns and more preferably an average particle size D50 value of 10 microns or smaller and ii) selecting a suitable alumina powder having a crystallite size of 300 A to 500 A, preferably between 325 A and 450A that does not need to be milled.
  • the alumina powder may include an acid incorporated into the alumina powder as a result of the alumina production process i.e. in situ.
  • an acid incorporated into the alumina powder as a result of the alumina production process i.e. in situ.
  • Sasol's Dispal® alumina product line or large crystallite aluminas such as Catapal® 200, have acid incorporated into the dry powder.
  • the liquid binder used for the method of the invention may comprise only water.
  • An acid may be added to the water if required, for example in the case of selecting the third option. When acid is added to the water up to 4% of the acid may be added to the water.
  • the liquid binder may include both water and an acid.
  • the acids preferably are monovalent acids. These monovalent acids may include nitric acid, formic acid, acetic acid, or mixtures thereof. Carboxylic acids with single or multiple acid sites may also be used. Acids such as lactic and tartaric are examples of these types of acids.
  • the amount of free liquid binder applied to the alumina powder to get it to form shaped alumina, for example beads, is defined by the weight of alumina powder divided by the weight of liquid binder applied. This is the alumina powder to liquid binder ratio.
  • the ratio of alumina powder to liquid binder ratio can be from 1.5:1 to as high as 15:1 on a weight basis.
  • Preferably the alumina powder to liquid binder ratio is between 1.8:1 and 10:1.
  • the calcination temperature may vary depending on the crystallite size of the alumina chosen and may be between 1250°C and 1700°C, preferably 1250°C to 1600X, more preferably 1250°C to below 1500°C.
  • the calcination may be carried out for a period of 1 hour to 40 hours. Calcination time of at least 6 hours is preferable.
  • the method may be either a batch process or a continuous process.
  • a shaped alumina produced according to the method(s) of the invention, the shaped alumina comprising, one, more than one, or, all, preferably more than one, and most preferably all of the following properties: i) a loose bulk density of greater than or equal to 1.20 g/ml, preferably greater than 1.65 g/ml
  • impurities of less than 5 ppm, preferably less than 3 ppm, and most preferably less than 2.5 ppm of any individual metal, and less than 9 ppm, preferably less than 7 ppm of impurities in total;
  • a shaped alumina comprising one, more than one, or, all, preferably more than one, and most preferably all of the following properties: i) a loose bulk density of greater than or equal to 1.20 g/ml, preferably greater than 1.650 g/ml,
  • the shaped alumina is preferably in the form of an agglomerate, a bead, a spherical particle, or a mixture thereof.
  • Figure 1 is a diagram of a high shear agglomeration process flow
  • Figure 2 is a diagram illustrating continuous flow high shear agglomeration
  • Figure 3 is a graph showing the effect of powder milling on shaped alumina i.e. bead strength
  • Figure 4 is a graph showing the effect of feed powder particle size on shaped alumina i.e. bead crush strength
  • Figure 5 is a graph showing the effect of initial powder particle size on loose bulk density
  • Figure 6 is a graph showing the effect of boehmite crystallite size on calcined shaped alumina i.e. bead strengths
  • Figure 7 is a graph showing the combined effect of calcining temperatures, crystallite size and powder milling on the strength of shaped alumina i.e. beads;
  • Figure 8 is a graph showing the change in surface area and porosity with calcining temperatures
  • Figure 9 is a graph showing a comparison of loose bulk density for shaped alumina i.e. beads produced with different boehmite crystallite sizes and different powder particle sizes at different calcining temperatures;
  • Figure 10 is a graph showing the comparison of loose bulk density for shaped alumina i.e. beads produced with different powder particle sizes (milled or unmilled) at various crystallite sizes;
  • Figure 11 is a graph showing the comparison of shaped alumina according to the invention i.e. bead strengths with commercial proppant strengths;
  • Figure 12 is a graph showing the crush strength of beads made with blended, milled alumina and Catapal® 200 with calcining temperatures of Example 4.
  • Figure 13 is a graph showing the loose bulk density of beads made with blended, milled alumina and Catapal® 200 with calcining temperatures of Example 4.
  • the invention describes a method to produce high strength shaped alumina by feeding alumina powder into an agglomerator having a central shaft, spraying liquid binder onto the alumina powder as it is displaced along a length of the shaft of the agglomerator to form shaped alumina.
  • the alumina can be in the form of agglomerates, beads, spherical particles, or combinations thereof.
  • the shaped alumina is then calcined.
  • Boehmite alumina powder is fed from an alumina powder feeder (10) to an inlet (12) of an agglomerator (14), being in this example a pin mixer.
  • the pin mixer (14) includes a chamber (16) and a central shaft (18) having mixers (20) thereon.
  • the mixers are preferably in the form of pins or paddles (not specifically shown) located along a length of the shaft (18).
  • the shaft (18) rotates continuously such that the mixers (20) are able to firstly break down an alumina powder and then re-agglomerate the alumina powder as the alumina powder is displaced along the length of the shaft (18) of the pin mixer (14).
  • the alumina powder comprises aluminum oxide hydroxide, a boehmite, or a pseudoboehmite, but is preferably a boehmite.
  • the alumina powder may as a first option have a crystallite size of 35 A to 190 A and a particle size Dso value of greater than or equal to 40 microns. In such a case the alumina powder may or may not include an acid in the alumina powder.
  • Such alumina powder is to be milled before being fed into the pin mixer to an average particle size Dso value of less than 40 microns, preferably 30 microns and more preferably 10 microns or smaller.
  • the alumina powder may have a crystallite size of 300 A to 500 A, preferably 325 A to 450 A.
  • Such alumina has an average particle size Dso value of 40 microns and may include an in situ acid in the alumina powder.
  • the invention provides for a third option, including a combination of i) milling the alumina powder having a crystallite size of between 35 A and 190 A and a particle size Dso value of greater than or equal to 40 microns to an average particle size Dso value of less than 40 microns, preferably an average particle size Dso value of 30 microns and more preferably an average particle size Dso value of 10 microns or smaller and ii) selecting a suitable alumina powder having a crystallite size of 300 A to 500 A, preferably between 325 A and 450 A that does not need to be milled.
  • the third option is a combination of the first and second options.
  • a liquid binder is sprayed onto the alumina powder(s) just after the powder(s) enters the pin mixer (14).
  • the liquid binder may either be water or a combination of water and acid(s) depending on what alumina powder is chosen for the method of the invention.
  • the acids preferably are monovalent acids. These monovalent acids may include nitric acid, formic acid, acetic acid or mixtures thereof. Carboxylic acids with single or multiple acid sites may also be used. Acids such as lactic and tartaric are examples of these types of acids.
  • the acid in the liquid binder acts to partially disperse some of the alumina powder.
  • the combination of water and acid(s) acting on the alumina creates a binder for the alumina.
  • alumina containing an acid water only may be used as the liquid binder since the acid function is already supplied in the powder feed. However, the invention does not preclude adding additional acid if required.
  • the acid added may be 5 wt%, preferably 4% or less of the liquid binder.
  • the liquid binder is dispersed into the alumina powder.
  • the alumina powder becomes partially dispersed making it adhesive and pliable.
  • the energy from the mixers (20) first breaks up the alumina powder and then forms it into shaped alumina including beads or spherical shapes through agglomeration. Beads are smoothed and rounded by the rotating action within the chamber. Moist shaped alumina in the form of beads, agglomerates, spherical particles, or mixtures thereof are formed and exit the mixer.
  • the beads can be sized by screening to obtain a product with a narrower particle distribution. These beads can be calcined at a calcination temperature of between 1250°C and 1700°C, preferably 1250°C to 1600°C, most preferably 1250°C to below 1500°C for a period of 1 to 40 hours, preferably at least 6 hours, without further drying.
  • the drying step as required by the prior art is no longer required if the method of the present invention is applied.
  • Figure 2 shows a detailed view of the pin mixer (14) of Figure 1.
  • the mixers (20) or rotating elements of the pin mixer (14) impart high energy into the alumina powder mixed with the liquid binder which accomplishes two actions; a) liquid binder is uniformly dispersed onto the alumina powder and b) the combined action of the acidic binder (either water and in situ acid of the alumina, or water and acid, or both) and high shear in the chamber causes the alumina powder to break down to small nuclei. These nuclei are then forced together by the mixing action and then agglomerate to form larger shaped alumina in the form of agglomerates, beads, spherical particles, or mixtures thereof which in turn are agglomerated to form even larger beads.
  • the acidic binder either water and in situ acid of the alumina, or water and acid, or both
  • the bead size is controlled by the ratio of alumina powder to liquid binder, the feed rate of powder which controls the time of agglomeration in the mixer, and the rotational speed of the rotor.
  • the ratio of alumina powder to liquid binder can be from 1.5:1 to as high as 15:1 on a weight basis. Preferably the ratio is between 1.8:1 and 10:1.
  • the pin mixer (14) shown in Figures 1 and 2 represents a continuous agglomerator. However, the process can be performed in a high shear agglomerator that operates batch wise for example.
  • Formic acid or nitric acid is used as an acid in the liquid binder.
  • An alumina powder to liquid binder ratio of 10:1 to 13:1 is used.
  • Shaped alumina in the form of beads in the size range of 100 microns to 2 mm in diameter can be made using appropriate powder feed rates and rotor speeds in the agglomerator.
  • the strength of the beads was measured by crush testing individual beads on a Mecmesin MultiTest 2.5i test stand between parallel plates. At least 25 beads were tested and the results averaged. The force required to crush each single bead was measured as was the diameter of the bead being tested. Crush strength of each bead was calculated as the crush force divided by the cross sectional area of the bead. The strength and diameter values were averaged for the sample of beads. Results are in psi and plotted against the mean diameter of the beads.
  • Milled Catapal B alumina refers to either of the two particle sizes created from the base alumina.
  • Table I Properties of Alumina Powders Used in the Examples
  • Alumina powder, Catapal ® B alumina, with a crystallite size of 47 A on the 021 plane and a particle size Dso value of 40 microns was used.
  • the alumina was milled by jet milling to an average particle size Dso value of 30 microns.
  • Formic acid diluted to 4% or lower concentration and water made up the liquid binder.
  • the alumina powder and liquid binder were run through the pin mixer and the beads that were produced were subsequently screened to size and calcined at 1450 °C for 10 hours to convert them to alpha alumina agglomerates/beads.
  • Example 2 The same process as per Example 1 was used except that the starting Catapal ® B alumina powder particle size was milled as per the invention, by jet milling the alumina powder to an average particle size D50 value of 10 microns.
  • Catapal ® 200 alumina with a crystallite size of 400 A was used. Because Catapal ® 200 has a crystallite size of 400 A, it was not milled. Catapal ® 200 alumina has formic acid incorporated into it, so this in situ formic acid was supplied as part of the powder feed.
  • the liquid binder was water alone.
  • the powder particle size D50 value was 40 microns.
  • Milled Catapal B was blended at 25% ratio with Catapal® 200.
  • the milled Catapal B had a particle size of 4 microns. Beads were processed with no acid.
  • the liquid binder was a blend of water and1% formic acid.
  • Figure 13 includes the bulk density and Figure 12 the crush strength of the blended material.
  • Alumina powder, unmilled Catapal ® B alumina, with a crystallite size of 47 A on the 021 plane and a particle size D50 value of 40 microns was used.
  • Formic acid diluted to 4% or lower concentration and water made up the liquid binder.
  • the alumina powder and liquid binder were run through the pin mixer and the beads that were produced were subsequently screened to size and calcined at 1450 °C for 10 hours to convert them to alpha alumina agglomerates/beads.
  • Comparative Example 3 The same process as per Comparative Example 1 was used except the beads were calcined at 1600 °C for 10 hours. Comparative Example 3
  • Alumina powder, unmilled Catapal ® B alumina, with a crystallite size of 47 A on the 021 plane and a particle size Dso value of 40 microns was used.
  • the liquid binder was nitric acid diluted to 2.5% or lower concentration and water.
  • the alumina powder and liquid binder were run through the pin mixer and the beads that were produced were subsequently screened to size and calcined at 1600 °C for 10 hours to convert them to alpha alumina agglomerates/beads.
  • Example 2 The same process as per Example 1 was used except that the starting alumina was unmilled Dispal ® 15N4 alumina (186 A). This product has nitric acid incorporated into the alumina during its production. In this example, only water was used as the liquid binder as the acid was in the alumina powder. The powder particle size Dso value was 40 microns.
  • Example 2 The same process as per Example 1 was followed except Catapal ® D alumina with a crystallite size of 77 A was substituted for Catapal ® B alumina.
  • the powder particle size Dso value was 40 microns.
  • Figure 3 shows the crush strength of beads from some of the Examples and Comparative Examples. Beads from each comparative example and example were screened to different sizes and then tested for crush strength. Mean strength was plotted as a function of the average bead diameter. A typical monotonic curve of crush strength (psi) decreasing with increasing bead diameter is shown by all the example data. Trend lines are included for reference for the unmilled Catapal ® B alumina beads calcined at 1450 °C and 1600 °C using formic acid and nitric acid as per Comparative Examples 1 and 3, respectively.
  • Figure 4 plots the particle size of the starting alumina powder (x-axis in microns) with the mean crush strength of the beads on the y- axis, (y axis in psi) .
  • Figure 4 shows mean crush strength for beads with the same average diameter plotted against the starting alumina powder mean particle size Dso value.
  • Calcining temperature was constant at 1450 °C with a residence time of 10 hours for all data.
  • the graph clearly shows the strength significantly increases.
  • the strength increase is not dependent upon the size of the agglomerated bead but rather on the particle size Dso value or diameter of the alumina powder fed into the pin mixer. Strength of all the bead sizes increases proportionately to the reduction in diameter of the feed powder.
  • Figure 4 clearly shows that milling the starting alumina powder to particle sizes Dso values of 30 microns and then 10 microns increases the bead crush strength for all samples. Also in Figure 4, data for two different alumina powder feeds is shown. Catapal® B powder has a crystallite size of 47 A (021 plane) and Catapal® D powder has a crystallite size of 77 A. However, milling the starting powder to a smaller initial size has a similar effect on both powders.
  • Figure 5 shows that the loose bulk density (hereinafter "LBD") of the beads is improved by the process of milling the alumina powder prior to feeding into the agglomerator.
  • LBD loose bulk density
  • An important advantage of the present invention is that there is an increase in LBD without the necessity of seeding the alumina with small alpha alumina particles to enhance sintering and densification. Seeding is an additional step that is difficult to perform. It requires intensive mixing of the seed and powder to ensure homogeneous distribution of the seed particles. The seeds must be produced to the correct size and quantity to get seeding effects and then mixed into the bulk powder. Seeding is a well- known process but difficult to perform effectively.
  • boehmite alumina with a crystallite size substantially larger than the first option of 35 A to 190 A i.e. as per the second option, in the range of 300 A to 500 A very high crush strength can be achieved without having to calcine the beads at extraordinarily high temperatures.
  • Figure 6 shows crush strength for beads formed and produced under similar conditions but using different crystallite size boehmite powders as feed as per Comparative Example 1 and Example 3.
  • the beads made from different crystallite size powders showed similar crush strength.
  • the very large Catapal ® 200 alumina shows a large increase in crush strength compared to Catapal ® B alumina (having a crystallite size of 47 A).
  • Using boehmite with a crystallite size larger than Catapal ® B alumina (47 A) gives much improved crush strength at temperatures which are more economical and easier to achieve than with small crystallite size boehmite.
  • the following may be employed: i) milling one of the smaller crystallite size aluminas, in the range of 35 A to 190 A, to a smaller particle size Dso value, or ii) using a large crystallite size alumina such as Catapal® 200, an alumina powder having a crystallite size of 300 A to 500 A, or iii) a combination of i) and ii).
  • a large crystallite size alumina such as Catapal® 200
  • an alumina powder having a crystallite size of 300 A to 500 A or iii) a combination of i) and ii).
  • These options produce an alumina bead having up to double the strength compared to beads made from unmilled small crystallite size boehmite (having a crystallite size between 35 A and 190 A). This strength can be achieved when the temperature of 1450 °C is used. The strength can be altered to the desired level by changing the calcining temperature in a range that is accessible with
  • the physical properties of the beads can be altered as needed for each application.
  • the surface area and porosity of beads formed from large crystallite size (400 A Catapal® 200) boehmite and smaller crystallite size, milled Catapal® D (77 A), milled to a particle size Dso value of 10 microns is shown as a function of the calcining temperature.
  • a wide range of surface area or pore volume can be achieved by altering the calcining temperature. While strength will generally increase with increasing temperature and conversely decreases with lower calcining temperature, the beads of the present invention already have high strength at lower temperatures and so other intrinsic properties can be altered without compromising bead strength.
  • desired intrinsic properties of the beads can be adjusted using the calcining temperature. Strength of the beads will be maintained during this process.
  • Loose Bulk Density is important for crucible fill in the synthetic sapphire industry. High bulk density is desired to maximize the fill weight in an individual crucible. This maximizes the production from a single crucible cycle and lowers costs.
  • Figure 9 shows the LBD of alumina beads made by altering the particle size D50 value and crystallite size of the feed alumina powder. Increasing the crystallite size or milling to a smaller particle size D50 value powder gives beads that have a LBD higher than smaller crystallite size alumina or unmilled powder. For unmilled powder, the graph shows that the LBD increases as the crystallite size is increased for the different calcining temperatures. When the alumina powders are milled, greater increases in the LBD are also seen.
  • LBD approaches 2.0 g/ml at the temperature of 1450 °C using milled Catapal ® B (particle size D50 value before milling 40 microns and after milling 10 microns) or milled Catapal ® D aluminas (particle size D50 value before milling 40 microns and after milling 10 microns).
  • Very large crystallite size alumina, Catapal ® 200 shows high LBD without milling when calcined at 1550 °C. Suitable selection of crystallite size combined as needed with powder milling can produce beads that with high LBD which will accordingly produce high fill weight.
  • Figure 10 shows the more dramatic effect of reducing the powder particle size D50 value by milling.
  • LBD results are plotted for a small range of crystallite size aluminas, from 47 A to 77 A. Increasing the alumina crystallite size gives a moderate increase in the LBD over the range. However, milling the powder prior to forming beads shows a large improvement in the LBD of the beads made from both the low and high end of the crystallite size range.
  • the Catapal ® B (47 A) produces nearly the same LBD as Catapal D (77 A) when both are milled to the particle size D50 value of 10 micron.
  • FIG. 1 1 Also shown in Figure 1 1 is the effect of increasing the crystallite size of the boehmite powder.
  • Normal Catapal® B alumina with 47 A crystallite size has significantly lower mean crush strength at any diameter than the representative proppant types.
  • Catapal® 200 with 400 A crystallite size gives beads that exceed the strength of the normal Catapal® B alumina and can be calcined to achieve strengths equal to or greater than the strongest commercial proppants shown in the chart.
  • a typical high strength commercial proppant, Carboprop® 20/40 is shown. Beads produced from Catapal® 200 alumina have strengths equivalent to this product.
  • Alumina Product Purity of the alumina is a critical issue for sapphire production.
  • Table II shows metals impurity analyses for a) the starting alumina powder, b) the uncalcined beads made by jet milling high purity boehmite and forming in the high shear agglomerator, and c) the beads after calcination. It can be seen that no or very low contamination of the product occurred through the process of the present invention. This low level of potential contamination makes the bead forming method suitable for production of high bulk density crucible fill for synthetic sapphire production processes.
  • the single forming step does not introduce metallic impurities into the alumina. Combined with the high bulk density that is easily obtained, the product is useful for making synthetic sapphire by crucible melting processes.
  • ND stands for non-detectable
  • Ultra High Purity Alumina Pural ® for example
  • Porosity of the beads can be controlled by controlling variables in both the feed and processing steps.
  • Final pore volume is adjusted by feed selection based upon the particle size, the agglomeration conditions, and the calcining temperature. Various combinations of these can be used singly or in concert to achieve the desired final porosity of the beads.
  • the beads described in this invention can be used as chemical carriers for oil field application, catalyst substrates, feed for various sapphire crystal forming methods that require free flowing, non-dusting particles or for crucible fill in sapphire production, and potentially as proppants for oil well applications

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